Synthesizing graphene from metal-carbon solutions using ion implantation

ABSTRACT

A method and semiconductor device for synthesizing graphene using ion implantation of carbon. Carbon is implanted in a metal using ion implantation. After the carbon is distributed in the metal, the metal is annealed and cooled in order to precipitate the carbon from the metal to form a layer of graphene on the surface of the metal. The metal/graphene surface is then transferred to a dielectric layer in such a manner that the graphene layer is placed on top of the dielectric layer. The metal layer is then removed. Alternatively, recessed regions are patterned and etched in a dielectric layer located on a substrate. Metal is later formed in these recessed regions. Carbon is then implanted into the metal using ion implantation. The metal may then be annealed and cooled in order to precipitate the carbon from the metal to form a layer of graphene on the metal&#39;s surface.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is related to the following commonly owned co-pendingU.S. patent application:

Provisional Application Ser. No. 61/156,991, “Synthesizing Graphene FromMetal-Carbon Solutions Using Ion Implantation,” filed Mar. 3, 2009, andclaims the benefit of its earlier filing date under 35 U.S.C. §119(e).

TECHNICAL FIELD

The present invention relates to semiconductor device fabrication, andmore particularly to synthesizing graphene from metal-carbon solutionsusing ion implantation.

BACKGROUND OF THE INVENTION

A material called graphene has recently been discovered to haveproperties believed to make it an excellent component of integratedcircuits. Graphene is a one-atom-thick planar sheet of sp²-bonded carbonatoms that are densely packed in a honeycomb crystal lattice. Thecarbon-carbon bond length in graphene is approximately 1.42 Å. Grapheneis the basic structural element of all other graphitic materialsincluding graphite, carbon nanotubes and fullerenes.

Currently, most graphene films are produced by exfoliation from naturalgraphite or are grown by thermal evaporation of silicon from singlecrystals of silicon carbide. Recently, attempts have been made to growgraphene on metal surfaces by introducing carbon to the metal usingchemical vapor deposition, such as exposing the metal surface tomethane. However, in the process of using chemical vapor deposition,hydrogen is present during the precursor stage which may lead to defectsin the graphene. Further, it is difficult to grow patterned mono layersof graphite (i.e., graphene) using this process. That is, it isdifficult to control the amount of carbon introduced in the metal usingthe process of chemical vapor deposition with precise dimensionalcontrol. In order to continue the progress towards developing smallerand more efficient semiconductor devices, growing graphene is highlydesired.

Therefore, there is a need in the art to introduce controlled quantitiesof carbon in a metal thereby more effectively growing graphene. Further,there is a need in the art for a process in growing graphene without thepresence of hydrogen to reduce the risk of defects in the graphene.

BRIEF SUMMARY OF THE INVENTION

In one embodiment of the present invention, a method for synthesizinggraphene comprises implanting carbon in a metal substrate via ionimplantation, where the carbon is distributed in the metal substrate.Further, the method comprises annealing the metal substrate with theimplanted carbon. Additionally, the method comprises cooling the metalsubstrate with implanted carbon after annealing in order to precipitatethe carbon from the metal to form a layer of graphene on a surface ofthe metal substrate. Additionally, the method comprises transferring themetal substrate with the layer of graphene onto a dielectric layer insuch a manner whereby the layer of graphene is placed on the dielectriclayer. Furthermore, the method comprises removing the metal substrate.

In another embodiment of the present invention, a semiconductor devicecomprises a silicon substrate, a dielectric layer on the siliconsubstrate and a graphene layer on the dielectric layer. The graphenelayer is formed by implanting carbon into a metal by ion implantation,where the carbon is precipitated by diffusion from the metal to form thegraphene layer on a surface of the metal via annealing and cooling themetal with the implanted carbon. The metal along with the layer ofgraphene is transferred onto the dielectric layer in such a mannerwhereby the layer of graphene is placed on the dielectric layer. Themetal is removed after the transfer of the metal and the layer ofgraphene onto the dielectric layer.

In another embodiment of the present invention, a method forsynthesizing graphene comprises patterning and etching a first set ofregions of a dielectric layer located on a silicon substrate. The methodfurther comprises depositing a metal barrier onto the dielectric layer.Additionally, the method comprises depositing a metal onto the metalbarrier forming a stack of metal/metal barrier. In addition, the methodcomprises annealing the metal/metal barrier stack. Further, the methodcomprises performing a chemical mechanical polishing of the metalfollowing the deposition of the metal onto the metal barrier whereby themetal resides in the first set of regions of the dielectric layer afterthe chemical mechanical polishing is performed. Furthermore, the methodcomprises patterning and etching photoresist mask regions to cover asecond set of regions of the dielectric layer, where the second set ofregions does not overlap with the first set of regions. In addition, themethod comprises implanting carbon in the metal via ion implantation,where the carbon is distributed in the metal. Furthermore, the methodcomprises removing the photoresist mask regions. Further, the methodcomprises annealing the metal with the implanted carbon. Further, themethod comprises cooling the metal with the implanted carbon afterannealing in order to precipitate the carbon from the metal by diffusionto form a layer of graphene on a surface of the metal.

In another embodiment of the present invention, a semiconductor devicecomprises a silicon substrate and a dielectric layer on the siliconsubstrate. The dielectric layer comprises a set of etched regionswhereby metal resides in the set of etched regions. A layer of grapheneresides on a surface of the metal after the carbon is introduced in themetal via ion implantation and after the metal with the implanted carbonis annealed and cooled to precipitate the carbon from the metal bydiffusion.

The foregoing has outlined rather generally the features and technicaladvantages of one or more embodiments of the present invention in orderthat the detailed description of the present invention that follows maybe better understood. Additional features and advantages of the presentinvention will be described hereinafter which may form the subject ofthe claims of the present invention.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

A better understanding of the present invention can be obtained when thefollowing detailed description is considered in conjunction with thefollowing drawings, in which:

FIG. 1 is a flowchart of a method for synthesizing graphene using ionimplantation of carbon in accordance with an embodiment of the presentinvention;

FIGS. 2A-D depict cross-sectional views of a semiconductor device duringthe fabrication of the steps described in FIG. 1 in accordance with anembodiment of the present invention;

FIG. 3 is an alternative method for synthesizing graphene using ionimplantation of carbon in accordance with an embodiment of the presentinvention; and

FIGS. 4A-F depict cross-sectional views of a semiconductor device duringthe fabrication of the steps described in FIG. 3 in accordance with anembodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention comprises a method and semiconductor device forsynthesizing graphene using ion implantation of carbon. In oneembodiment of the present invention, carbon is implanted in a metalusing ion implantation. After the carbon is distributed in the metal,the metal is annealed and cooled in order to precipitate/segregate thecarbon from the metal by diffusion to form a layer of graphene on thesurface of the metal. The metal/graphene surface is then transferred toa dielectric layer located on a substrate (e.g., silicon with adielectric) in such a manner that the graphene layer is placed on top ofthe dielectric layer. The metal layer is then removed, such as via wetetching. In another embodiment of the present invention, recessedregions are patterned and etched in a dielectric layer located on asubstrate (e.g., silicon). After depositing the metal barrier onto thedielectric layer, metal is deposited onto the metal barrier. Thesemiconductor device is then planarized using chemical mechanicalpolishing thereby leaving metal only in the recessed regions.Photoresist mask regions are then formed to cover the exposed regions ofthe dielectric layer (i.e., cover all parts of the dielectric layerexcept the metal in the recessed regions). Carbon is then blanketimplanted into the metal. The photoresist is then removed via aphotoresist stripping technique. The metal with the implanted carbon maythen be annealed and cooled in order to precipitate the carbon from themetal to form a layer of graphene on the surface of the metal.

As discussed in the Background section, currently, most graphene filmsare produced by exfoliation from natural graphite or are grown bythermal evaporation of silicon from single crystals of silicon carbide.Recently, attempts have been made to grow graphene on metal surfaces byintroducing carbon to the metal using chemical vapor deposition, such asexposing the metal surface to methane. However, in the process of usingchemical vapor deposition, hydrogen is present during the precursorstage which may lead to defects in the graphene. Further, it isdifficult to grow patterned mono layers of graphite (i.e., graphene)using this process. That is, it is difficult to control the amount ofcarbon introduced in the metal using the process of chemical vapordeposition with precise dimensional control. In order to continue theprogress towards developing smaller and more efficient semiconductordevices, growing graphene is highly desired. Therefore, there is a needin the art to introduce controlled quantities of carbon in a metalthereby more effectively growing graphene. Further, there is a need inthe art for a process in growing graphene without the presence ofhydrogen to reduce the risk of defects in the graphene.

Controlled quantities of carbon may be introduced into the metal therebymore efficiently growing graphene as well as growing graphene withoutthe presence of hydrogen using the principles of the present inventionas discussed below in connection with FIGS. 1, 2A-D, 3 and 4A-F. FIG. 1is a flowchart of a method for synthesizing graphene using ionimplantation. FIGS. 2A-D depict cross-sectional views of thesemiconductor device during the fabrication steps described in FIG. 1.FIG. 3 is a flowchart of an alternative method for synthesizing grapheneusing ion implantation. FIGS. 4A-F depict cross-sectional views of thesemiconductor device during the fabrication steps described in FIG. 3.

Referring to FIG. 1, FIG. 1 is a flowchart of a method 100 forsynthesizing graphene using ion implantation in accordance with anembodiment of the present invention. FIG. 1 will be discussed inconjunction with FIGS. 2A-D, which depict cross-sectional views ofsemiconductor device 200 during the fabrication steps described in FIG.1 in accordance with an embodiment of the present invention.

Referring to FIG. 1, in conjunction with FIGS. 2A-D, in step 101, carbon201 is implanted into a metal substrate 202 (e.g., copper, nickel,cobalt, iron, zinc, solid solution of the aforementioned metals,ruthenium, platinum, etc.) using ion implantation as illustrated in FIG.2A. In one embodiment, during the implantation of carbon 201 into metalsubstrate 202, dopants (e.g., boron) (not shown in FIG. 2A) may beintroduced into metal substrate 202. Carbon 201 is distributed (notshown in FIG. 2A) in metal substrate 202 based upon one or moreparameters of ion implantation, such as energy, flux and angle.

In step 102, metal substrate 202, with the implanted carbon 201, isannealed. In one embodiment, metal substrate 202 is annealed usingisothermal annealing. In another embodiment, metal substrate 202 isannealed using rapid thermal annealing.

In step 103, metal substrate 202, with the implanted carbon 201, iscooled after annealing in order to precipitate/segregate carbon 201 frommetal 202 by diffusion to form a layer of graphene 203 on the surface ofmetal substrate 202 as illustrated in FIG. 2B. As used herein,“precipitate” refers to separating or segregating carbon 201 from metal202.

In step 104, metal substrate 202, along with the layer of graphene 203,are transferred onto a dielectric layer 204 in such a manner whereby thelayer of graphene 203 is placed on the surface of dielectric layer 204as illustrated in FIG. 2C. In one embodiment, dielectric layer 204 mayreside on a silicon substrate 205 as illustrated in FIG. 2C. Further, inone embodiment, dielectric layer 204 is a layer of silicon dioxide.Dielectric layer 204 may further include high-k dielectrics, such asSiON, ZrO₂, ZrSiO, ZrLaO, ZrAlO, ZrSiON, ZrLaON, ZrAlON, LaLuO, LaLuON,and hafnium based dielectrics, such as but not limited to HfO₂, HfSiO,HfLaO, HfAlO, HfSiON, HfLaON, HfAlON, HfZrO, HfZrON and hafniumzirconate (Hf_(x)Zr_(1-x)O₂).

In step 105, metal substrate 202 is removed as illustrated in FIG. 2D.In one embodiment, metal substrate 202 is removed using wet etching.

Method 100 may include other and/or additional steps that, for clarity,are not depicted. Further, method 100 may be executed in a differentorder presented and the order presented in the discussion of FIG. 1 isillustrative. Additionally, certain steps in method 100 may be executedin a substantially simultaneous manner or may be omitted.

In another embodiment, a layer of polymethyl methacrylate (“PMMA”) orpolydimethlysiloxane (“PDMS”) is deposited onto the graphene/metalstack. The metal is removed by chemical etching and then thePMMA/graphene layer or PDMS/graphene layer is transferred onto asubstrate, such as silicon dioxide/silicon. After the transfer, the PMMAor PDMS can be chemically removed to expose the graphene.

An alternative embodiment for synthesizing graphene using ionimplantation is discussed below in connection with FIGS. 3 and 4A-F.FIG. 3 is a flowchart of an alternative method 300 for synthesizinggraphene using ion implantation in accordance with an embodiment of thepresent invention. FIG. 3 will be discussed in conjunction with FIGS.4A-F, which depict cross-sectional views of semiconductor device 400during the fabrication steps described in FIG. 3 in accordance with anembodiment of the present invention.

Referring to FIG. 3, in conjunction with FIGS. 4A-F, in step 301, adielectric layer 401 is patterned and etched to form recesses 402A-Bextending to the barrier of a silicon substrate 403 as illustrated inFIG. 4A. Recesses 402A-B may collectively or individually be referred toas recesses 402 or recess 402, respectively. While FIG. 4A depicts tworecesses 402 being formed, any number of recesses 402 may be formed fromdielectric layer 401. In one embodiment, dielectric layer 401 is a layerof silicon dioxide.

In step 302, a metal barrier 404, such as tantalum, tantalum nitride,titanium, titanium nitride, ruthenium or any other appropriate barrierfor the selected carbon host metal, is deposited onto dielectric layer401, including over recesses 402 in dielectric layer 401, as illustratedin FIG. 4A.

In step 303, a metal 405 (e.g., copper, nickel, cobalt, iron, zinc,solid solution of the aforementioned metals, ruthenium, platinum, etc.)is deposited onto metal barrier 404 as illustrated in FIG. 4B.

In step 304, the metal stack (metal 405/metal barrier 404) is annealedto increase the grain size of the carbon host metal.

In step 305, a chemical mechanical polishing of semiconductor device 400is performed following the deposition of metal 405 onto metal barrier404 in order to planarize the surface as illustrated in FIG. 4C.

In step 306, semiconductor device 400 is patterned and etched to formphotoresist mask regions 406A-C to cover exposed regions of dielectriclayer 401 as well as open vias 409A-B to metal contacts 405 asillustrated in FIG. 4D. Vias 409A-B may collectively or individually bereferred to as vias 409 or via 409, respectively. Further, photoresistmask regions 406A-C may collectively or individually be referred to asphotoresist mask regions 406 or photoresist mask region 406,respectively. It is noted that any number of vias 409 or photoresistmask regions 406 may be formed and that FIGS. 4A-F are illustrative.

In step 307, carbon 407 is implanted (blanket implant) into metal 405via ion implantation as illustrated in FIG. 4D. In one embodiment,during the implantation of carbon 407 into metal 405, dopants (e.g.,boron) (not shown in FIG. 4D) may be introduced into metal 405. In oneembodiment, carbon 407 is implanted into the non-masked areas usingvertical ion implantation. In one embodiment, carbon 407 is distributedin metal 405 based upon one or more parameters of ion implantation, suchas energy, flux and angle as illustrated in FIG. 4E.

In step 308, photoresist mask regions 406 are removed by wet chemicalmeans and the surface of metal 405 is cleaned as illustrated in FIG. 4E.In one embodiment, photoresist mask regions 406 are removed via aphotoresist stripping technique, including organic stripping, inorganicstripping and dry stripping.

In step 309, metal 405, with the distributed carbon 407, is annealed. Inone embodiment, metal 405 is annealed using isothermal annealing. Inanother embodiment, metal 405 is annealed using rapid thermal annealing.

In step 310, metal 405, with the distributed carbon 407, is cooled afterannealing in order to precipitate/segregate carbon 407 from metal 405 bydiffusion to form a layer of graphene 408 on the surface of metal 405 asillustrated in FIG. 4F.

In step 311, graphene 408 is transferred to another substrate (notshown) or used as a seed to grow graphene 408 over the surface ofdielectric layer 401 using chemical vapor deposition.

Method 300 may include other and/or additional steps that, for clarity,are not depicted. Further, method 300 may be executed in a differentorder presented and the order presented in the discussion of FIG. 3 isillustrative. Additionally, certain steps in method 300 may be executedin a substantially simultaneous manner or may be omitted.

Although the method and semiconductor device are described in connectionwith several embodiments, it is not intended to be limited to thespecific forms set forth herein, but on the contrary, it is intended tocover such alternatives, modifications and equivalents, as can bereasonably included within the spirit and scope of the invention asdefined by the appended claims.

1. A method for synthesizing graphene, the method comprising: implantingcarbon in a metal substrate via ion implantation, wherein said carbon isdistributed in said metal substrate; annealing said metal substrate withsaid implanted carbon; cooling said metal substrate with said implantedcarbon after said annealing in order to precipitate said carbon fromsaid metal to form a layer of graphene on a surface of said metalsubstrate; transferring said metal substrate with said layer of grapheneonto a dielectric layer in such a manner whereby said layer of grapheneis placed on said dielectric layer; and removing said metal substrate.2. The method as recited in claim 1 further comprising: introducingdopants into said metal substrate during said implantation of saidcarbon in said metal substrate.
 3. The method as recited in claim 1,wherein said carbon is distributed in said metal substrate based uponone or more of the following parameters of said ion implantation:energy, flux and angle.
 4. The method as recited in claim 1, whereinsaid metal substrate is annealed using isothermal annealing.
 5. Themethod as recited in claim 1, wherein said metal substrate is annealedusing rapid thermal annealing.
 6. The method as recited in claim 1,wherein said dielectric layer comprises one of the following: silicondioxide, SiON, ZrO₂, ZrSiO, ZrLaO, ZrAlO, ZrSiON, ZrLaON, ZrAlON, LaLuO,LaLuON, and hafnium based dielectric, wherein said dielectric layer islocated on a silicon substrate.
 7. The method as recited in claim 1,wherein said metal substrate is removed via wet etching.
 8. The methodas recited in claim 1, wherein said metal substrate comprises one of thefollowing: copper, nickel, cobalt, iron, zinc, a solid solution ofaforementioned metals, ruthenium and platinum.
 9. A semiconductordevice, comprising: a silicon substrate; a dielectric layer on saidsilicon substrate; and a graphene layer on said dielectric layer,wherein said graphene layer is formed by implanting carbon into a metalvia ion implantation, wherein said carbon is precipitated by diffusionfrom said metal to form said graphene layer on a surface of said metalvia annealing and cooling said metal with said implanted carbon, whereinsaid metal along with said layer of graphene is transferred onto saiddielectric layer in such a manner whereby said layer of graphene isplaced on said dielectric layer, wherein said metal is removed aftersaid transfer of said metal and said layer of graphene onto saiddielectric layer.
 10. The semiconductor device as recited in claim 9,wherein said dielectric layer comprises one of the following: silicondioxide, SiON, ZrO₂, ZrSiO, ZrLaO, ZrAlO, ZrSiON, ZrLaON, ZrAlON, LaLuO,LaLuON, and hafnium based dielectric.
 11. The semiconductor device asrecited in claim 9, wherein said metal comprises one of the following:copper, nickel, cobalt, iron, zinc, solid solution of aforementionedmetals, ruthenium and platinum.
 12. A method for synthesizing graphene,the method comprising: patterning and etching a first set of regions ofa dielectric layer located on a silicon substrate; depositing a metalbarrier onto said dielectric layer; depositing a metal onto said metalbarrier forming a stack of said metal/metal barrier; annealing saidmetal/metal barrier stack; performing a chemical mechanical polishing ofsaid metal following said deposition of said metal onto said metalbarrier whereby said metal resides in said first set of regions of saiddielectric layer after said chemical mechanical polishing is performed;patterning and etching photoresist mask regions to cover a second set ofregions of said dielectric layer, wherein said second set of regionsdoes not overlap with said first set of regions; implanting carbon insaid metal via ion implantation, wherein said carbon is distributed insaid metal; removing said photoresist mask regions; annealing said metalwith said implanted carbon; and cooling said metal with said implantedcarbon after said annealing in order to precipitate said carbon fromsaid metal by diffusion to form a layer of graphene on a surface of saidmetal.
 13. The method as recited in claim 12 further comprising:introducing dopants into said metal during said implantation of saidcarbon in said metal.
 14. The method as recited in claim 12, whereinsaid dielectric layer comprises a layer of silicon dioxide.
 15. Themethod as recited in claim 12, wherein said metal barrier comprises oneof the following: titanium, titanium nitride, tantalum and tantalumnitride.
 16. The method as recited in claim 12, wherein said metalcomprises one of the following: copper, nickel, cobalt, iron, zinc, asolid solution of aforementioned metals, ruthenium and platinum.
 17. Themethod as recited in claim 12, wherein said carbon is distributed insaid metal based upon one or more of the following parameters of saidion implantation: energy, flux and angle.
 18. The method as recited inclaim 12, wherein said metal/metal barrier stack is annealed usingisothermal annealing.
 19. The method as recited in claim 12, whereinsaid metal/metal barrier stack is annealed using rapid thermalannealing.
 20. The method as recited in claim 12 further comprising:transferring said layer of graphene to a substrate to grow furtheramounts of graphene.
 21. The method as recited in claim 12 furthercomprising: growing further amounts of graphene using said layer ofgraphene as a seed.
 22. A semiconductor device, comprising: a siliconsubstrate; and a dielectric layer on said silicon substrate, whereinsaid dielectric layer comprises a set of etched regions whereby metalresides in said set of etched regions, wherein a layer of grapheneresides on a surface of said metal after carbon is introduced in saidmetal via ion implantation and after said metal with said implantedcarbon is annealed and cooled to precipitate said carbon from said metalby diffusion.
 23. The semiconductor device as recited in claim 22,wherein said dielectric layer comprises a layer of silicon dioxide. 24.The semiconductor device as recited in claim 22, wherein said metalcomprises one of the following: copper, nickel, cobalt, iron, zinc,solid solution of aforementioned metals, ruthenium and platinum.